Large, hydrophilic polyoxoanions with high solubility in water and/or other polar solvents demonstrate unique solution behavior by self-assembling into single layer, hollow, spherical “blackberry” structures, which is obviously different from small, simple ions. These macroions cannot be treated as insoluble colloidal suspensions because they form stable “real solutions”. Counterion-mediated attraction is considered as the main driving force for the self-assembly behavior. The size disparity between the macroions and their counterions results in macroion–counterion pairing which leads to the inter-macroanionic attraction. The blackberries, with robust membranes semi-permeable to cations, can adjust their size accurately and reversibly in response to the change of solvent polarity and charge density of individual macroions. The inorganic macroions with well-defined size, shape, mass, charge density, but no intramolecular interactions, are ideal model systems to study the intermolecular interactions in polyelectrolyte and bio-macromolecular solutions. The blackberry structures show certain similarities to spherical viral capsids, from the overall structure to the formation kinetics. More amazingly, these inorganic macroions demonstrate some features usually believed to belong only to complex biological molecules, such as the self-recognition in dilute solutions. Meanwhile, polyoxometalates-based organic–inorganic hybrid materials demonstrate amphiphilic properties by self-assembling into vesicles and reverse vesicles in polar and non-polar solvents, respectively, and form monolayer at the water/air interface. Different from conventional amphiphiles, these hybrids show pH-dependent and counterion-dependent self-assembly behaviors with controllable functionality, e.g. fluorescence and catalytic activity, due to the high and tunable charges and the functionalities of POM polar head groups.